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+ ) (
a a constant to account for the existence of mutual attraction between the molecules.
a/v
2
the force of attraction
b the coefficient introduced to account for the volumes of molecules, and is known as
co-volume
c
c
p
T R
a
c
c
p
T R
b
Tc Critical temperature
pc Critical pressure
Unique feature
Van der Waals equation qualitatively accounts for the heating effect observed at
ordinary temperatures.
Limitations
The values of a and b (which are assumed to be constant) are found to vary with
temperature. Thus the results obtained from the equation are incorrect when the
variation of a and b is large with respect to temperature.
The equation is not accurate enough in the critical region.
Virial expansions
The virial expansion, also called the virial equation of state, is the most interesting
and versatile of the equations of state for gases. The virial expansion is a power series in
powers of the variable, B/V, and has the form,
+ + + +
p A p A p A A
RT
pv
o
+ + + +
v
B
v
B
v
B
B
RT
pv
o
The coefficient, Ao, A1, A2, . and Bo, B1, B2, .. are called the virial coefficients
and are functions of temperature. Ao, Bo are first virial coefficient and A1, B1 are second virial
coefficients and so on.
Law of corresponding states
For each substance there is a compressibility factor. It would be very convenient if
one chart could be used for all substances. The general shapes of the vapour dome and of
the constant temperature lines on the p-v plane are similar for all substances, although the
scales may be different. This similarity can be exploited by using dimensionless properties
called reduced properties.
Reduced pressure,
c
r
p
p
p
Reduced temperature,
c
r
T
T
T
Reduced volume,
c
r
v
v
v
Generally for all substances, vr = f(pr, Tr) and Z = f(pr, Tr)
The relation among the reduced properties, pr, Tr and vr is known as the law of
corresponding states.
Compressibility
In thermodynamics and fluid mechanics, compressibility is a measure of the relative
volume change of a fluid or solid as a response to a pressure (or mean stress) change.
p
v
v
K
----- (1)
where v is specific volume and p is pressure. The above statement is incomplete, because
for any object or system the magnitude of the compressibility depends strongly on whether
the process is adiabatic or isothermal. Accordingly we define the isothermal compressibility
as:
T
T
p
v
v
K
,
_
----- (2)
where the subscript T indicates that the partial differential is to be taken at constant
temperature. The adiabatic compressibility as:
S
S
p
v
v
K
,
_
----- (3)
where S is entropy. For a solid, the distinction between the two is usually negligible.
Coefficient of volume expansion is defined as,
p
T
v
v
,
_
----- (4)
The inverse of the compressibility is called the bulk modulus.
We know that,
,
_
,
_
,
_
V
p T
p
T
T
v
v
p
----- (5)
p
T
v
v
,
_
from (4)
T
T
p
v
v K
,
_
from (2)
Substituting in (5), ( )
,
_
,
_
V T
T
p
T
v
v K
V T
T
p
K
,
_
----- (6)
Compressibility Chart
The compressibility factor (Z) is used to alter the ideal gas equation to account for the
real gas behaviour. The compressibility factor is usually obtained from the compressibility
chart. Mathematically, it is defined as,
ideal
actual
v
v
T R
v p
Z
p the pressure,
v the specific volume of the gas,
T the temperature, and
R the gas constant.
Z = 1 for ideal gas
Critical compressibility factor,
c
c c
c
T R
v p
Z
Z can, in general, be either greater or less than unity for a real gas. The deviation
from ideal gas behavior tends to become particularly significant (or, equivalently, the
compressibility factor strays far from unity) near the critical point, or in the case of high
pressure or low temperature. In these cases, a generalized Compressibility chart or an
alternative equation of state better suited to the problem must be utilized to produce accurate
results.
Rules on partial derivatives
Theorem 1 (Exact differential)
If a relation exists among the variables x, y and z, then z may be expressed as
function of x and y.
z = f (x, y)
dy
y
z
dx
x
z
dz
x
y
,
_
+
,
_
Let,
y
x
z
M
,
_
and
x
y
z
N
,
_
dy N dx M dz +
Differentiating M partially with respect to y, and N with respect to x,
y x
z
y
M
x
,
_
x y
z
x
N
y
,
_
y
x
x
N
y
M
,
_
,
_
,
_
,
_
f f
f
x
z
z
y
y
x
Theorem 3
Among the variables x, y and z, any one variable may be considered as a function of
the other two.
If x = x (y, z) y = y (x, z) z = z(x, y)
,
_
,
_
,
_
z y
z
z
y
x
z
y
x
Among the thermodynamics variables, p, v and T, the following relation holds good.
,
_
,
_
,
_
V
p T
p
T
T
v
v
p
Maxwells equations
A pure substance existing in a single phase has only two independent variables. Of
the eight quantities, p, v, T, s, u, h, F (Helmholts function) and G (Gibbs function), any one
may be expressed as a function of any two others.
(i) Consider a non flow process.
q = w + u
dq = dw + du
du = dq dw
= T ds p dv ----- (1)
Therefore, u = f (s, v)
dv
v
u
ds
s
u
du
S V
,
_
+
,
_
----- (2)
Comparing (1) and (2)
V
s
u
T
,
_
and
S
v
u
p
,
_
s v
u
v
T
S
,
_
and
v s
u
S
p
S
,
_
But,
,
_
,
_
v s
u
s v
u
Therefore,
V S
s
p
v
T
,
_
,
_
I Maxwell equation
The rate of increase in temperature with respect to volume during isentropic process
is equal to the rate of decrease in pressure with respect to entropy during constant volume
process.
(ii) Consider a flow process.
q = w + h
dq = dw + dh
dh = dq dw
= T ds + v dp ----- (1)
Therefore, h = f (s, p)
dp
p
h
ds
s
h
dh
S
p
,
_
+
,
_
----- (2)
Comparing (1) and (2)
p
s
h
T
,
_
and
S
p
h
v
,
_
s p
h
p
T
S
,
_
and
p s
h
s
v
p
,
_
But,
,
_
,
_
p s
h
s p
h
Therefore,
p
S
s
v
p
T
,
_
,
_
II Maxwell equation
The rate of increase in temperature with respect to pressure during isentropic process
is equal to the rate of decrease in volume with respect to entropy during constant pressure
process.
(iii) F = u Ts
dF = du (T ds + s dT)
= du T ds s dT
But, du = T ds p dv
Therefore, dF = T ds p dv T ds s dT
= - p dv s dT ----- (1)
Therefore, F = f (v, T)
dv
v
F
dT
T
F
dF
T V
,
_
+
,
_
----- (2)
Comparing (1) and (2)
V
T
F
s
,
_
and
T
v
F
p
,
_
T v
F
v
s
T
,
_
and
v T
F
T
p
V
,
_
But,
,
_
,
_
v T
F
T v
F
Therefore,
V T
T
p
v
s
,
_
,
_
,
_
+
,
_
----- (2)
Comparing (1) and (2)
p
T
g
s
,
_
and
T
p
g
v
,
_
T p
g
p
s
T
,
_
and
p T
g
T
v
p
,
_
But,
,
_
,
_
p T
g
T p
g
Therefore,
p
T
T
v
p
s
,
_
,
_
IV Maxwell equation
The rate of increase in entropy with respect to pressure during isothermal process is
equal to the rate of decrease in volume with respect to temperature during constant pressure
process.
TdS equations
(i) Let s = f (T, v) T and v independent variables
dv
v
s
dT
T
s
ds
T V
,
_
+
,
_
------ (1)
Let u = f (T, v)
dv
v
u
dT
T
u
du
T V
,
_
+
,
_
dv
v
u
dT C
T
V
,
_
+
------ (2)
Also, du = T ds p dv ------ (3)
Equating (2) and (3),
dv
v
u
dT C dv p ds T
T
V
,
_
+
dv p
v
u
T
dT
T
C
ds
T
V
1
]
1
+
,
_
+
------ (4)
Comparing (1) and (4),
T
C
T
s
V
V
,
_
------ (5)
From Maxwell III-equation,
V T
T
p
v
s
,
_
,
_
------ (6)
Substituting (5) and (6) in (1),
dv
T
p
dT
T
C
ds
V
V
,
_
+
dv
T
p
T dT C ds T
V
V
,
_
+
First T ds equation
We know that,
V T
T
p
K
,
_
dv
K
T dT C ds T
T
V
,
_
+
First T ds equation
(ii) Let s = f (T, p) T and p are independent variables
dp
p
s
dT
T
s
ds
T
p
,
_
+
,
_
------ (1)
Let h = f (T, p)
dp
p
h
dT
T
h
dh
T
p
,
_
+
,
_
dp
p
h
dT C
T
p
,
_
+
------ (2)
Also, dh = T ds + v dp ------ (3)
Equating (2) and (3),
dp
p
h
dT C dp v ds T
T
p
,
_
+ +
dp v
p
h
T
dT
T
C
ds
T
p
1
1
]
1
,
_
+
------ (4)
Comparing (1) and (4),
T
C
T
s
p
p
,
_
------ (5)
From Maxwell IV-equation,
p
T
T
V
p
S
,
_
,
_
------ (6)
Substituting (5) and (6) in (1),
dp
T
v
dT
T
C
ds
p
p
,
_
dp
T
v
T dT C ds T
p
p
,
_
Second-T ds equation
We know that,
p
T
v
v
,
_
p
T
v
v
,
_
dp v T dT C ds T
p
Second T ds equation
(iii) Let u = f (p, v) p and v are independent variables
dv
v
u
dp
p
u
du
p
V
,
_
,
_
------ (1)
V
V
v
p
T
T
u
p
u
,
_
,
_
,
_
T
v
K
C ------ (2)
Also, u = h pv
p
v
h
v
u
p p
,
_
,
_
p
v
T
T
h
p p
,
_
,
_
p
v
C
p
------ (3)
Substituting (2) and (3) in (1),
dv p
v
C
dp
K
C du
p
T
v 1
]
1
+
------ (4)
We know that T ds = du + p dv
dv p dv p
v
C
dp
K
C ds T
p
T
v
+
1
]
1
+
dv
v
C
dp
K
C
p
T
v
+ ------ (5)
dv
v
C dp
K
C ds T
p
T
V
+
Third T ds equation
Change in internal energy
du = T ds p dv
dv
T
p
T dT C ds T
V
V
,
_
+
First T ds equation
dv p dv
T
p
T dT C du
V
V
,
_
+
dv p
T
p
T dT C du
V
V 1
]
1
,
_
+
Internal energy of an ideal gas is function of temperature only
dv p
T
p
T dT C du
V
V 1
]
1
,
_
+
For an ideal gas, p v = R T
v
T R
p
T
p
v
R
T
p
v
,
_
dT C dV p
T
p
T dT C du
v
V
V
1
]
1
,
_
+
Therefore the internal energy is depending only on temperature.
Change in internal energy when a gas obeys Van der Waals equation
We know that, dv p
T
p
T dT C du
V
V 1
]
1
,
_
+
Van der Waals equation is, T R b v
v
a
p
,
_
+ ) (
v
a
b v
T R
p
b v
R
T
p
v
,
_
Therefore, dv
v
a
b v
T R
b v
R
T dT C du
V 1
]
1
,
_
dv
v
a
dT C du
V
1
]
1
v
dv
a dT C du
V
1
]
1
+
) (
v v
a T T C u u
V
Change in entropy when a gas obeys Van der Waals equation
dv
T
p
T dT C ds T
V
V
,
_
+
First T ds equation
dv
T
p
T
dT
C ds
V
V
,
_
+
Van der Waals equation is, T R b v
v
a
p
,
_
+ ) (
v
a
b v
T R
p
b v
R
T
p
v
,
_
Therefore, dv
b v
R
T
dT
C ds
V
,
_
+
+
b v
dv
R
T
dT
C ds
V
,
_
,
_
b v
b v
R
T
T
C s s
v
ln ln
Change in enthalpy
dh = T ds + V dp
dp
T
v
T dT C ds T
p
p
,
_
Second T ds equation
dp v dp
T
v
T dT C dh
p
p
+
,
_
dp v
T
v
T dT C dh
p
p
1
1
]
1
,
_
dp
T
v
T v dT C dh
p
p
1
1
]
1
,
_
+
Enthalpy of an ideal gas is function of temperature only
dp
T
v
T v dT C dh
p
p
1
1
]
1
,
_
+
For an ideal gas, p v = R T
p
T R
v
T
v
p
R
T
v
v
,
_
dT C dp
T
v
T v dT C dh
p p
1
]
1
,
_
+
Therefore the enthalpy is depending only on temperature.
Difference in heat capacities (Cp Cv)
To derive
T p
v p
v
p
T
v
T C C
,
_
,
_
or (Cp Cv) = R or
T
v p
K
v T
C C
Note: Derive First and Second T ds equations and proceed as follows:
dv
T
p
T dT C ds T
V
V
,
_
+
First T ds equation
dp
T
v
T dT C ds T
p
p
,
_
Second T ds equation
Equating the above equations,
dv
T
p
T dT C
V
V
,
_
+
dp
T
v
T dT C
p
p
,
_
( ) dp
T
v
T dv
T
p
T dT C C
p v
v p
,
_
+
,
_
dp
T
v
C C
T
dv
T
p
C C
T
dT
p v p v v p
,
_
,
_
+
,
_
,
_
----- (1)
We can write, T = f (p, v)
dv
v
T
dp
p
T
dT
p
V
,
_
,
_
----- (2)
Comparing (1) and (2),
v v p p
T
p
C C
T
v
T
,
_
,
_
----- (3)
From (3),
p v
v p
T
v
T
p
T C C
,
_
,
_
----- (4)
But,
,
_
,
_
,
_
T
p v
p
v
v
T
T
p
T p v
v
p
T
v
T
p
,
_
,
_
,
_
----- (5)
Substituting (5) in (4),
T p
v p
v
p
T
v
T C C
,
_
,
_
----- (6)
p v = R T
p
T R
v
p
R
T
v
p
,
_
----- (7)
v
T R
p
v
T R
v
p
T
,
_
----- (8)
Substituting (7) and (8) in (6),
v p
T R
v
T R
p
R
T C C
v p
,
_
p v = R T
R
T R
T R
C C
v p
Cp Cv = R ----- (9)
We know that,
p
T
v
v
,
_
v
T
v
p
,
_
T
T
p
v
v
K
,
_
T
T
K v
p
v
,
_
----- (10)
Ratio of heat capacities
Note: Derive First and Second T ds equations and proceed as follows:
dv
T
p
T dT C ds T
V
V
,
_
+
First T ds equation
dp
T
v
T dT C ds T
p
p
,
_
Second T ds equation
Consider isentropic process, ds = 0
dp
T
v
T dT C
p
p
,
_
dT
dp
T
v
T C
p
p
,
_
dv
T
p
T dT C
V
V
,
_
dT
dv
T
p
T C
V
V
,
_
dv
dT
dT
dp
p
T
T
v
C
C
v
p v
p
,
_
,
_
dv
dp
p
T
T
v
C
C
v
p v
p
,
_
,
_
But,
s
v
p
dv
dp
,
_
,
_
,
_
,
_
----- (1)
We can write,
,
_
,
_
,
_
T
p v
p
v
v
T
T
p
T
p v
p
v
v
T
T
p
,
_
,
_
,
_
Substituting in (1),
s
T
v
p
v
p
p
v
C
C
,
_
,
_
----- (2)
T
T
p
v
v
K
,
_
T
T
K v
p
v
,
_
S
S
p
v
v
K
,
_
S
S
K v
p
v
,
_
Substituting in (2),
S
T
v
p
K
K
C
C
----- (3)
Joule-Thomson coefficient
A gas is made to undergo continuous throttling process by a valve, as shown. The
pressures and temperatures of the gas in the insulated pipe upstream and downstream of
the valve are measured with suitable manometers and thermometers.
h
J
p
T
,
_
Joule-Thomson expansion
Let p1 and T1 be the arbitrarily chosen pressure and temperature before throttling and let
them be kept constant. By operating the valve manually the gas is throttled successively to
different pressures and temperatures. These are then plotted on the T-p coordinates. The
curve passing through all these points is an isenthalpic curve.
Isenthalpic state of a gas
Isenthalpic curves and the inversion curve
The initial pressure and temperature of the gas (before throttling) are then set to new
values, and by throttling to different states, a family of isenthalpes is obtained for the gas.
The curve passing through the maxima of these isenthalpes is called the inversion curve.
The numerical value of the slope of an isenthalpe on a T-p diagram at any point is
called the Joule-Thomson coefficient and is denoted by J.
At inversion curve, J = 0
At right side of the inversion curve, dT is positive, dp is negative.
J = - ve (Heating region)
At left side of the inversion curve, dT is negative, dp is negative.
J = + ve (Cooling region)
dp v ds T dh + ----- (1)
Second T ds equation is given by,
dp
T
v
T dT C ds T
p
p
,
_
Substituting in (1),
dp v dp
T
v
T dT C dh
p
p
+
,
_
dp v
T
v
T dT C
p
p
1
1
]
1
,
_
The second term in the above equation stands only for a real gas, because for an ideal gas,
dh = Cp dT
dh = 0 for isenthalpic process
Therefore,
1
1
]
1
,
_
dp v
T
v
T dT C
p
p
dp v
T
v
T dT C
p
p
1
1
]
1
,
_
1
1
]
1
,
_
v
T
v
T
C dp
dT
p p
1
1
]
1
,
_
,
_
v
T
v
T
C p
T
p p
h
Therefore,
1
1
]
1
,
_
,
_
v
T
v
T
C p
T
p p
h
J
1
]
1
,
_
,
_
v
T
v
T
C p
T
p
h
J
,
_
,
_
v
T
v
T
C p
T
p p
h
J
But,
p
T
V
V
,
_
[ ] [ ]
T
C
v
v v T
C
p p
J
T
,
_
,
_
fg
fg
f v
f g
v
h
v v
s s
dv
ds
dT
dp
,
_
,
_
,
_
+ + +
c
n n n n ..........
n
n
x
n
n
x
Partial volume of component-1,
p
T R n
p
T R m
V
u
Mass of component-1, m1 = M1 n1 = mf1 m
Gas constant of component-1, R = Ru/M1
R1 = Characteristic gas constant (J/kgK)
M1 = Molar mass (Molecular weight) of component-1
n1 = Number of moles of component-1
p, T, V
n
1,
n
2
,
mf1 = Mass fraction of component-1
Mass of gas mixture, m = m1 + m2 + + mc
Volume of gas mixture, V = V1 + V2 + + Vc
Internal energy of mixture,
c
c c
m m m
u m u m u m
u
+ + +
+ + +
.........
..........
Enthalpy of mixture,
c
c c
m m m
h m h m h m
h
+ + +
+ + +
.........
..........
Specific heat of mixture,
c
pc c p p
p
m m m
C m C m C m
C
+ + +
+ + +
.........
..........
c
vc c v v
v
m m m
C m C m C m
C
+ + +
+ + +
.........
..........
Molar mass of mixture,
c
c c
n n n
M n M n M n
M
+ + +
+ + +
.........
..........
c c x
M x M x M x + + + .. ..........
Gas constant of mixture,
M
R
m m m
R m R m R m
R
u
c
c c
+ + +
+ + +
.........
..........
Density of mixture,
T R
p
Specific heat ratio of mixture,
c c
x x x + + + .. ..........
Note: Molecular weight of the mixture is also called as apparent molecular weight.